Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



controlled conditions from mineral oil, such as crude 2,771,433 Patented Nov. 20., 1.956

residues obtained by the elimination of the aldehydic 2,771,433 oxygen atom; the divalent radical PROCESS FOR BREAKING PETROLEUM- EMUL- H H SIONS EWLOYING CERTAIN .POLYEPOXIDE g-g; TREATED DERIVATIVES OBTAINEDBY REAC- TIQN' 0F MONOEPOXIDES WITH RESINS thedivalent Melvin De Groote, University City, andKwan-Ting Shen, i

Brentwood, Mo., assignors to "Petrolite Corporation,

Wilmington, Del., a corporationof Delaware No Drawing. Application ApriLZZ, 1953, Serial No. 350,534

20 Claims, (Cl. 252338) radical, the divalent sulfone radical, and the divalent monosulfide radical --S, the divalent radical CHzSCHzand the divalent disulfide radical SS-; and R10 is the divalent radical obtained by thev elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol The present invention is a continuation-in-part of our copending' application, Serial No. 305,079, filed August 18, 1952, now abandoned.

Our invention provides an economical and rapid proon cess for resolving petroleum emulsions of the water-in- I I oil type that are commonly referred to as cut oil, I E roily oil, emulsified oil, etc., and'which comprise fine droplets of naturally-occurring waters or brines disin which and represent hydrogen and hydro- P i a more 16.58 permallsintslagfi throughout the carbon substituents of the aromatic nucleus, said suboil which constitutes the continuous phase of the invenim member h i not over 18 carbon atoms, ti'on. A further limited aspect of the invention is represented also provldes an 0301111031 n rapid Promss for by the use of such products of reaction wherein the separating emulsions which have been prepare under oxyalkylated resin condensate is reacted with a member of the class of (a) compounds of the following formula oils and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under thecor ditions ust mentioned are of significant value H20 Rn in removing impurities, particularly inorganic salts, from pipeline oil. 0 2

Attention is directed to two co-pending De Groote ap- 3 wherein R is essentially an aliphatic hydrocarbon bridge, plications, Serial No. 310,554, filed September 19,1952, each n independently has one of the values 0 to 1, and now Patent No..2,695,890 and Serial No. 333,389,. filed R1 is an alkyl radical containing from 1 to 4 carbon January 26,1953. These two applications described hyatoms, or even 12 carbon atoms, and (b) cogenerically drophile products obtained bythe oxyalkylation of the associated compounds formed in the preparation of (a) condensates of certain phenol-aldehyde resins with respect preceding, including monoepoxides. to hydroxylated polyamines and formaldehyde. Reference to being thermoplastic or non-thermosetting The present invention is concerned with breakingwatercharacterized products as being liquids at ordinary temin-oil emulsions by the use of-products obtained by-reperature or readily convertible to liquids by merely acting said oxyalkylated derivatives of the. kind just deheating below the point of pyrolysis andv thus differentiates scribed withaphenolic polyepoxide of the kind previously them from infusible resins. Reference to being soluble described in our aforementioned co-pendingapplication, in 311 Organic Solvent means y of the 1151131 Organic Serial No. 305,079. solvents, such as alcohols, ketones, esters, ethers, mixed Thus the present invention is concerned with the use of Solvents, Reference to Solubility is rely to difproducts of reaction obtained by a 3-step manufacturing ferent'iate from a reactant which is not soluble and might process involving (1) condensing certain phenol aldehyde be not only insoluble but also infusible. Furthermore, resins, hereinafter described in detail, with certain basic. solubility is a factor insofar that it is sometimes desirable hydroxylated polyamines, hereinafter described indetail, to dilute the compound containing the epoxy rings beandformaldehyde; (L oXyalk-ylation of the condensation fore reacting with the monoepoxide-derived product. In product with certain monoepoxides,,hereinafter described such instances, of course, the solvent selected would have in detail; and (3) oxyalkylationof the previously oxyto be one which is not susceptible to oxyalkylation, as alkylated resin condensate with certain phenolicpolyfor example, kerosene, benzene, toluene, dioxane, variepoxides, hereinafter describedin detail, and co-genericous ketones, chlorinate solvents, dibutyl ether, dihexylally associated compounds formed in'the rv preparation. ether, ethyleneglycol diethylether, diethyleneglycol di- A 0 limited aspect of the P s nvention is c m ethylether and dimethoxytetraethyleneglycol. cerned with the use of such products of reaction wherein The expression epoxy is not usually limited to the the oxyalkylated resin condensate is reacted with a mem- LZ-epoxy i Th LZ-epoxy i i Sometimes r f rred ber of the class of compounds of the following formula: to as the oxirane ring to distinguish it from other epoxy 0 H 0,--,--o-c-- OR1[R]..R1OCC..C 0Ri-[R].R10-o-o -0 H! H Hi H: A) H: Ha-Hv H:

in whichR represents a divalent radicalselected from rings. Hereinafter the word epoxy unless indicated the class consisting of ketone residues formed by the otherwise, will be used to mean the oxirane ring, i. e., elimination of the ketonic oxygen atom. and aldehyde the l, 2.-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxy rings or oxirane rings in the alpha-omega position. This is a. departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest 5 20 times their weight of 5% gluconic acid at ordinary temdiepoxide which contains at least 4 carbon atoms and is perature and show at least some tendency towards being formally described as l,2-epoXy-3,4-epoxybutane(l,2-3,4 self-dispersing. The solvent which is generally tried is diepoxybutane). xylene. Ifxylene alone does not serve then a mixture of It well may be that even though the previously sug- Xylene and methanol, for instance, 80 parts of xylene and gested formula represents the principal component, or 10 20 Parts of methanol, T 70 Parts Of Xyl ne and 30 P s components, of the resultant or reaction product deof methanol, can be used. Sometimes it is desirable to scribed in the previous text, it may be important to note add a mall amount of acetone to the xylene-methanol that somewhat similar compounds, generally of much mixture, for instance, to of acetone. As oxyhigher molecular weight, have been described as complex alkylation proceeds the significance of the basicity of any resinous epoxides which are polyether derivatives of nitrogen group is obviously diminished. polyhydric phenols containing an average of more For purpose of resolution of petroleum emulsions of than one epoxide group per molecule and free from functhe water-in-oil type, we particularly prefer to use those tional groups other than epoxide and hydroxyl groups. products which as such or in the form of the free base See U. S. Patent No. 2,494,295, dated January 10, 1950, or hydrate, i. e., combination with water or particularly to Greenlee. The compounds here included are limited in the formof a low molal organic acid salt such as the to the monomers or the low molal members ofsuch series gluconates or the acetate or hydroxy acetate, have sufliand generally contain two epoxide rings per molecule ciently hydrophile character to at least meet the test set and may be entirely free from a hydroxyl group. This forth in U. S. Patent No. 2,499,368, dated March 7, 1950, is important because the instant invention is directed to De Groote et al. In said patent such test for emulsificatowards products which are not insoluble resins and have ti E g a water-insoluble solvent, generally xylene, is certain solubility characteristics not inherent in the usual d ib d as an i d f ff i i thefmqsetting F In the present instance the various condensationprodflg Obtamed a reactant having generally 2 P Y ucts as such or in the form of the free base or in the form rings depifled in the last formula PFeceding, 9 of the acetate, may not necessarily be xylene-soluble molal polymers thereof, it becomes obvious the reaction although they are in many instances If Such compounds take Place Wlth any Oxyalkylated phenol'aldehyde are not xylene-soluble the obvious chemical equivalent F by vlrtuF of the fact h there are always present or equivalent chemical test can be made by simply using f P11611011c hydroxyl rafilcals or alkanol Fadlcals some suitable solvent, preferably a water-soluble solvent suiting g the oxyalkylanon of phenohc hydroxyl such as ethylene glycol diethylether or a low molal alradlcals there be Present reactwe hydrogen atoms cohol, or a mixure to dissolve the appropriate product :lttached to a img i atom or an oxygen g g i being examined and then mix with the equal weight of mg on Whether mmal y thin-e was present a y foxy ate xylene, followed by addition of water. Such test is obgroup attached to an amino hydrogen group or.a sec- 1 th f th h h b ondary amino group. In any event there is always amultivlous y or reason t at t e Y plicity of reactive hydrogen atoms present in the 40 phases on vigorous shalqng and surface activity maltes its alkylated amine modified pheno1 a1dehyde resin presence manifest. It is understood the reference 1n the T 0 illustrate the products which represent the subject hereto P t= clamls as to the use 9 the Xylene m matter of the present invention reference will be made the emulslficanon test mclfldes such f to a maction involving a mole of the oxyalky'lafing agent, For purpose of convenience, what 18 said hereinafter i. e., the compound having two oxirane rings and an f l be divided into nine Paris with Part in turn, being oxyalkylated amine condensate. Proceeding with the exdlvlded into three Subdivisions! ample previously described it is obvious the reaction Part 1 is c ncerned with our preference in regard to ratio of two moles of the oxyalkylated amine condensate the polyepoxide and particularly the diepoxide reactant; to one mole of the oxyalkylating agent gives a product Part 2 is concerned with certain theoretical aspects of which may be indicated as follows: diepoxide preparation;

in which the various characters have their previous significance and the characterization oxyalkylated condensate is simply an abbreviation for the oxyalkylated condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free'base (combination with water) or a salt form such as the ace-- tate, chloride, etc. The purpose in this instance is to difierentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances Where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides;

Part 7 is concerned with the oxyalkylation of the products described in Part 6, preceding;

Part 8 is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated amine-rnodified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed outpreviously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molol polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united direetly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrates a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availabiliy and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. Th formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for theother would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and etfect to the other classes of epoxide reactants.

if sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorinehappened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 The polyepoxides and particularly the diepoxides canbe derived by more than one methol as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the folowing structure:

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Cl OH CH3 Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difficulty stems from a number .ferred ratio, to wit, two parts of epichlorohydrin to one and as a result one may obtain products in which more of sources and a few of the more important ones are as follows:v

'8 spond in every respect except that one terminal epoxide group is absent and in its place is a group having one v chlorine atom and one hydroxyl group, or else two hy- (1) The closing ofthe epoxy ring involves the use of droxyl groups, or an unreacted phenolic ring.

caustic soda or the like which, in turn, is an effective (5) some reference has been made to thp presence a D catalyst m causing the mug to Open m an Oxylakylatlon a chlorine atom and although all effort is directed toreaction. I

Actually What may happen for any one of a number wards the elimination of any chlorine-containing moleof reasons is that one obtains a product in which there cule yet It Is apparnt that t i Often an Ideal approach rather than a practical possibility. Indeed, the same sort o ls only one ep Xlde nng and there as a matter of of reactants are sometimes employed to obtaln products a gi g 56855 2 12 2 g gs g radlcal as Illustrated in which intentionally there is both an epoxide group and H I H H (3H3 H H H dated January-8, 1952, to Zech. HC-OCOCC OCCCH For purpose of brevity, without going any further, the 6 15 next formula is in essence one which, perhaps in an or e idealized way, establishes the composition of resinous products available under the name of Epon Resins as now sold in the open market. See, also, chemical pamphlet entitled Epon Surface-Coating Resins, Shell Chemical Corporation, New York city. The word Epon is a registered trademark of the Shell Chemical Corporation.

(EH3 (I)H ([3113 (2) Even if one starts with the reactants in the pre- For the purpose of the instant invention, n may represent a number including zero, and at the most a low number such as 1, 2 or 3. This limitation does not exist in than two epichlorohydrin residues become attached to a i actual efforts to obtain resins as differentiated from the single bis-phenol A nucleus by virtue of the reactive herein described soluble materials. It is quite probable hydroxyls present which 7 enter into oxyalkylation rethat in the resinous products as marketed for coating use actions rather than ring closure reactions. the value of n is usually substantially higher. Note (3) As is well known, ethylene oxide in the presence of again what has been said previously that any formula is, alkali, and for that matter in the complete absence of at best, an over-simplification, or at the most represents water, forms cyclic polymers. Indeed, ethylene oxide 40 perhaps only the more important or principal constituent can produce a solid polymer. This same reaction can, or constituents. These materials may vary from simple and at times apparently does, take place in connection non-resinous to complex resinous epoxides which are with compounds having one, or in the present instance, polyether derivatives of polyhydric phenols containing an two substituted oxirane rings, i. e., substituted 1,2 epoxy average of more than one epoxide group per molecule rings. Thus, in many ways it is easier to produce a polyand free from functional groups other than epoxide and mer, particularly a mixture of the monomer, dimer and hydroxyl groups. trimer, than it is to produce the monomer alone. Insummary then in light of what has been said, corn- (4) As has been pointed out previously, monoepoxides pounds suitable for reaction with amines may be summay be present and, indeed, are almost invariably and marized by the following formula:

part of bis-phenol A, they do not necessarily so react I in! I a/II l Liz/II u n R R R inevitably present when one attempts to produce polyor for greater simplicity the formula could be restated epoxides, and particularly diepoxides. The reason is the thus:

0 0-o OR -[R],.-R1OG(' J-C OR1-[R],.R1OCC-O Hg H H2 Hz 6H H2 H: H HI in which the various characters have their prior significance and in which R10 is the divalent radical ob- 5 tained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol H d d g oC ho d-i ic rt H I H \O/ OH one which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as I may react with a mole of bis-phenol A to give a mono- L, epoxy structure. Indeed, in the subsequent text imme diately following reference is made to the dimers, trimers in which R, R, and R represent hydrogen and hydroand tetramers in which two epoxide groups are present carbon substituents of the aromatic nucleus, said sub- Needless to say, compounds can be formed which gorrestituent memhp; having not over 18 carbon atoms; P-

a chlorine atom present. See U. S. Patent No. 2,581,464,

resents an integer selected from the class of zero and l,

w I Purely by way of illustration, the following diepoxides, and n represents a whole number not greater than 3.

- or diglycidyl ethers as they are; sometimes termed, are RT 3 included for purpose of illustration. These particular SubdivisioWA compounds are described in the two patents just The preparations of the diepoxy derivatives of th'edi- 5 me tio TABLE I Ex- 7 Patent;

ample Diphenol Dtglycidyl ether refernumber a i once CHQ(CQH|OH)1 cDi(epoxypropoxyphenyl)methane 2, 506, 486 CHSCH (CH4OH);. Di(epoxypropoxyphenyl)methylmefihanefi 2, 506, 486 (CH3)10(CIH4OH)L Di(epoxypropoxyphenyl)d1methylmethane 2, 506, 486 CzHaC(CH;)(OtH4OH)1 Di(cpoxypropoxyphenyl)ethylmethylmethane. 2, 506, 486 (C:H5);0(GH4OH),. Di(epoxypropoxyphcnyl)diethylrnethane c. 2, 506, 486 Di(e oxy ropoxyphenyl)methyipropylmethan 2,- 506,486 Di(epoxypropoxyphenyhmethylphenylmethane 2, 506, 486 Di(epoxypropoxyphen '1) ethylph'enylmethane 2, 506, 486 Di(epoxypropoxyphenyl)propylphen lmethan 2, 506, 486 D'Kepoxypropoxyphenyl)bntylpheny methane 2, 506, 486 Di(epoxypropoxyphenyntolylmethane M 2, 506, 486 (CH;ClH4)C(CH;) (OIHO Di(epoxypropoxy'phenyl)tolylmethylmethane. 2, 506, 486 Dihydroxy diphenyl. 4,4-bis(2,3-epoxypropoxy)diphenyL.-, 2, 530, 353 (GH;)C(C|H .C H|OH');1 2,2bis(4-(2,3-epoxyprop0xy)Z-tertlafybutyl pheuympropene '2,- 530, 353

phenols, which are sometimes referred to as diglycidyl Subdivision B ethers, have been described in a number of patents. For 25 A t th preparation of low-molal polymeric e'poxides com/wince, reference will be made t0 two only, t0 Wit, or mixtures reference is made to aforementioned U. S.

aforementioned U. S. Patent 2,506,486, and aforemenpatents 2 575,553 d 2,532 935,

iiOned a In light of U. S. Patent No. 2,575,558, the following examples can be specified by reference to the formula 30 therein provided one still bears in mind it is in essence an over-simplification;

TABLE II o C CC OR1[R].. B O-C -CC -O R1[R],.R1OCCC H: H H: H: l a H: H- 4 H:-

OH n' (in which the characters have their previous significance) Example --R O- from HR OH R n 11 Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bis-phenol A. Low polymeric mixture about %or more ....c wheren=0, remainderlargely' Where I {n'==1, some where 'Il'=2. CH:

B2 do CH, 1 0,1,2 Phenol known as bis-phenolB. See note l regarding B1 above.

l ([211: CH:

B3 Orthobutyiphenol it, CH; 1 0,1,2 Even though 1: is preferably 0, yet the usual reaction product might well con C- tain materials where n is 1,- or to a lesser degree 2. CH:

B4 Orthoamylphenol (EH; 1 0,1,2 Do.

I CH5 B5 Orthooctylphenol ([111; 1 0,1,2 Do.

. (I]. OH:

B6 Orthononylphenoi (3H, 1 0,1,2 Do.

B7 0rthododecylphenui i (EH; 5 1- 0,1,2 Do.

B8.; -Metacres'o1". i CH3: 1- 0,1,2 S'eje prior note; This phenol usedas v mitielmaterial is known as bis-phenol c... 0. For other'suitable bis phenolssee 1 U S. Patent 2,504,191. a

' .TABLE 11 (continued) 2 Example R O-irom HmoH -R-- 'n n Remarks number Bo fin CH; 1 0,1,2 Seepriornote. I r .l

(5H, CH: B10 Dlbntyl (ortho-pere) phenol- 1g 1 0,1,2 Do.

311 Diemyl(ortho-para) phenol. lg 1 0,1,2 Do.

B12 Dioctyl (ortho-para) phenol- 13 1 0,1,2 Do.

B13 Dinonyl (ortho-para)pheno1 1g 1 0,1,2 Do. H

1314 Diamyl (ortho-pam) phenolg 1 0,1,2 Do.

I CH;

1215 do 13 1 0,1,2 Do.

I CIHI B16 Hydroxy benzene 1 0,1,2 Do.

B17 Diamyl phenol (ortho-pare)- -SS- 1 0,1,2 Do.

Rm rin -B- V 1 0,1,2 Do.

B19 Dibntylphenol (ortho-para). 1g 1 0,1,2 Do. H ,7 i 1320-.-.-- -.ao.'-'..;-'.; .l n n 1 0.1.2 Do.

H H B21 DinonylphenoKortho-para). 1g 1g 1 o, 1,2 Do.

322....-- Hydroxy benzene fil) 1 0,1,2 Do.

3 an Non 0 0,1,2 Do.

324..-.-- Ortho-isopropyl phenol OH; 1 0,1,2 See prior note. As to preparation of 4,4- l isopropylidene bis-(2-isopropylphenol) see U. 8. Patent No. 2,482,748, dated I Sept. 27, 1949, to Dietzler. CH:

1325-...-. Para-octyl phenol C Ha-S-C Hz 1 0, 1, 2 See prior note. (As to preparation or the phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et al.)

B26 Hydroxybenzene CH: 1 0,1,2 Seeprlor note. (As to pre ration olthe phenol sulfide see U. Patent No. l l

E l 02H;

Subdivision C to numerous other diphenols which can be readily con- The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking raxiical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless offthe nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed verted to a suitable polyepoxide, and particularly diepoxide, reactant. I

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of eyclohexylphenol or phenylphenol.

75 Such substituents are usually in the ortho position and 13 may be illustrated by a phenol of the following composition:

HO OH Similar phenols which are monofunctiona'l, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other samples include:

a CH:

wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains .at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the -CsHi1 groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

CaHn CuHn See U. S. Patent No. 2,285,563.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545."

14 on on R: R1 3 t 1%.

CH3 CH3 wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

OH=OH 0H 0:011 011 See U. S. Patent No. 2,515,908. I As to sulfides, the following compound is of interest:

Cs u OuHn OH OH See U. S. Patent No. 2,3 31,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly com pounds suchas Alkyl AlkyI Alkyl Alkyl in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH OH; OH; OH

R: R1 R1 R2 in which R1 and R2 are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R1 and R2 each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfides, disulfides, and polysulfides.

PART 4 It is well known that one can readilypurchase on the open market, or prepare, fusible, organic solvent-soluble,

15 water-insoluble resin polym rs of a composition approximated in an idealized form by the formula In the :above formula n represents :a i small iwho'leinunzber amyl, hexyl, decyl or dodecyl radical. Where the divalent 7 bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms. or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previouslynoted. However, even when obtainedfrom a difunctional phenol, for instance, para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent,.such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote andKeiser. 3

The resins herein employed as raw materials must be solubl'e:in anonoxygenated solvent, s'uchasbenzeneor xylene. "This presents .no problem-insofanthat' all that is required is to make a solubility-test on commercially available-resins, or else prepare resins whichare xylene or benzenersolubleas described in aforementioned U. "S, Patent No. 2;'499,365, or in U. 8'. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser; In sai'd. patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyd'e resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic'nuclei per resinmolecule. These resins are difunctional only'in regard to methylol-forming reactivity, are derived by reaction betweena difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in thesubstantial absence of'tn'functional phenols. Thephenol is of the formula in which R is 'an aliphatic hydrocarbon. radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in' the"2,4,'6, position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of. formaldehyde and two moles-of. a basic nonhydroxylated secondary amine as specified, followingthe same idealized 0ver-sirnplificationpreviously re,- ferred' to, theresultantproduct mightbe illustrated thus:

7 7 16 EThm-basic nonhydroxylated 'iamine' irray acbe 'designctt thus: a l

V V .n'.

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine'with the resin molecule, or even to a very slight extent, if at all,;2;resin units;may combine without any famine in the reaction product, :as indicated in 'the following fformulas z.

viously mentioned U. S. Patent 2,499,368.

pointed out previously, asifar astheqresin: unit goes one can usea mole-of aldehydeother than formaldehyde,.such as ac'etaldehyde, propionaldehyde or 'butyraldehyde. Theresin unit may be exemplified thus:

in which R' is the divalent radical obtained from the particular aldehyde employed to form; the resin. For reasons which are obvious the condensation product obtained appears tube-described best in terms of the method of manufacture.

As previously stated th preparation of resins, the .kindherein employed as reactants, is'weliknown. Seepre Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid .nor basic properties'in the ordinary sense or without any catalyst at al. It is'preferable that the resins employed be substantially neutral. In other words, if'prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found However, the most desirable procedure-in practically every case is to have the resin neutral.

In preparing resins one does not get'a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc- It is usually a mixture; for

instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional valnefor n..as,;.for.exainple, 3.5, 4.5 or 5.2.

i'In. the. actual .manufaeture .of the ."resins we found no.

reason, for .using. other than those. which -are .lowest .in. price andmost readily availableconamercially. pun

17 pose of convenience suitable resins are characterized in the following table:

TABLE III M01. wt. EX- R!!! of resin ample R Position derived n molecule number of R from (based on n+2) Phenyl Para. 3. 5 992. 5

Terti but 1 do 3. 5 S82. 5 My y 3. 5 882. 5 3. 5 1, 025. 5 3. 5 959. 5 3. 5 805.5

Terti am 1 3. 5 1,022. 5 Nony l zujhn 3. 5 1,330. 5 Tertiary butyl do Butyr- 3. 5 1,071. 5

aldehyde Tertiary amyl 3. 5 1,148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

Tertia am 1 3. 5 1, 085.5 Nonyl l lnfl nfl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1,083. 4 Nonyl 4. 2 1, 430. 6 4. 8 1, 094. 4 4. 8 1, 189.6 4. 8 1, 570. 4 1. 5 604. 1.5 646. 0 1. 653. 0 1. 5 688.0

2. 0 692. 0 2. 0 748. 0 Cycl do 2. 0 740.0

PART 5 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyamine 'having at least one secondary amino radical, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alkylcyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxylation of low cost polyamines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of example the following formulas are in.- cluded. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

C211; CIHAOH CaHs CzHs

Another procedure for producing suitable polyamines is a reaction involving first an alkyleneimine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus the second-introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide'so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, one can obtain a series of primary amines 19 and corresponding secondary amines which are characterized by the fact that such amines include groups havingrepetitious ether linkages and thus intr'oduce'a defiinite hydrophile effect'by virtue of the ether linkage. Suitable, polyether amines susceptible to conversion in the manner described include thoseof the formula /NH Ln' in which x is a small whole number having a value of 1 or more, and may be as much as or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to l,

with the proviso that the sume of m plus in equals 2;.

and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943 to Hester, and 2,355,337 dated August 8, 1944, to

Spence. The latter patent describes typical haloalkyl ethers such as CH30C2H4C1 OH:CH2

CH2 CH-CHzOCzHiOCgHgBl' Other similarsecondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to 'Jones et a1. 7 In the above formulaR may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary aminies which can be converted into appropriate polyamines can be obtained from products which are sold in the 'open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 1949, to Kaszuba, provided :there-is no negative group or halogen attached to the phenolic nucleus. Examples include the following; beta phenoxyethylamine, gamma phenoxypropylamine, beta phenoxy alpha --methylethy lamine, and beta-phenoxypropylamine. v v I Other secondary monoamines .suitable for conversion into polyamines are'the kind described in British Patent No. 456,517, and may be illustrated by 1 In light of the various examples of'polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown simplification. currence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radi cal contains twoor more secondary amino groups the amine may be reactive at two different positions and thus the same amine may yield compounds in which R and R are dissimilar.

0 H3 CH:

In the first of the two above formulas if thereaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than v if the reaction took place at the intermediate secondary amino radical as difierentiated from the terminal group. Again, referring to the second formula above, although a'terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united 'to the.

methylene bridge, depending on whether the reaction took place at'either one of the two outer secondary. amino groups, or at the central secondary amino group. If there are two points of reactivity towards formalde-- hyde as illustrated by the above examples it is obviousthat one might get a mixture in which in part the reactiontook place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:; a

' :CH; CH3

'N CzHtN C2H4NC2H4N C2H4N I H. H H

H V CrHiOH orrtNHoH ,cnrNnonroornon VCHIINHQHQ veer-en, I p CHPCH: H oqm o-Nn-onzonrNn-on no-on 'CHPC I CH:C 1

with the statement that such presentation is an over- It was pointed out that at least one oc- As is well known one can prepare ether amino alcohols of the type in which R represents an alkyl group varying from methy] to normal decyl, and in fact, the group may contain asmany as 15, or even carbon atoms. See J. Org. Chem., 17, 2 (1952).

Over and above the specific examples which have appeared previously, attention is directed to the fact that -a number of suitable amines are included in subsequent Table IV.

PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a. condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained' are not heat-convertible and since manufacture is not: restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary 22 overv and above what has been said previously, in, light of subsequent examples. However, for purpose of claritythe following, details are included.

A convenient'piece of equipment for preparation of these cogeneric mixtures is a resinpot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to bee solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or. a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing. such solvents are not here included as raw materials. The, reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a lowboiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols. can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not re= quired in the sense that it isnot necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system. for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used forany subsequent reaction. However, if the reaction mass is: going to. be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexylalcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol. shouldnot be used or else it should be. removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage 'for reasons stated.

The products obtained, depending on the. reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making asolution in. the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxy-acetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing. with benzene or the like.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is.used initially the period is not critical, infact, it. may be anything from a few hours up to 24' hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantagein holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction 'mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as'to use up part of the formaldehyde atsuch lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes iteasier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are' mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubilityis not necessary as previously pointed out but may be convenient'under certain circumstances. On the other hand, if the products are not mutuallyisoluble then agitation should bemore vigorous for the reason that reaction probably takes place principally at the in-' terfaces and the more vigorous the agitation the more interfacial area. The general a procedure employed 1 is invariably the same when adding the resin and the selected solvent, such asben zene or xylene. Refiuxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However if the resin is prepared as such it may be added in solution form, just as preparation is described in afore-. mentioned U. S. -Patent 2,49 9,368. After theiresin is in complete solution the polyamine is added and; stirred.

7 Depending on the polyamine selected, itmay or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble inthe aqueous formaldehyde solution. If so, the resin then will dis-i solve in the formaldehyde solution as-added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solu tion, or mechanical mixture,- if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial 'low temperature stage isemployed. The formaldehyde is then-'added'in' a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial'37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution 'of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formalde hyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss,

On a large scale if there is any ditficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. Thereaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion,.foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using'solid formaldehyde because even here water of reaction is formed. 7 7

Returning again to the preferred method of reaction and particularly. from the standpointof laboratory pro: cedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reac-' tion mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, we then come plete the reactionby raising the temperature up to 150v C., or thereabouts as required. The initial low tempera- 24 ture procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range.

This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, 'as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other ,cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in adilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if .any is present, is another index.

In light of what has been said previously little more need be said as to the actual procedure employed for the preparation of, the herein described condensation products. The following examplewill serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a paratertiary butylphenol' and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at'the end of the reaction. The molecular weight of the resin was; 882.5. This corresponded-to an average of about 3 /2- phenolic nuclei as the value for n which excludes the 2 externalnuclei,1i;'e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser-weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine .were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added-in a little over 3 hours. The mixture wasstirred vigorously and kept within a temperature range of 33 to 48 C. for about 17'hours'. At the end of this time it was refluxed usinga phase-separating trap and a small amount ofaqueous distillate withdrawn from time to time. 'The presence of formaldehyde was noted. Any unreacte d formaldehyde seemed to disappear within about'3 hours 'or ther'eabouts.' As soon as the odor of formaldehyde was-no lorigerparticularly noticeable or detectable the phase-separating trap was'set so as to eliminate partof the xylene was removed until the temperature reached approximately 150 C." or perhaps a little'higher. The reaction mass was kept at this'temperature for a littie over 4 hours'and the reaction stopped. 'During this time any additional water, which was probably water of Amine reaction which had formed, was eliminated by means of H p the trap. The residual xylene was permitted to stay 1n CH2 CH2' (IE-H2 the cogeneric mixture. A small amount of the sample HO CH HC OH was heated on a water bath to remove the excess xylene. 5 OH OH CH CH The residual material was dark red in color and had the 2 2 2 2 consistency of a sticky fluid or tacky res1n. The overall CH3 H MCZHOHM time for reaction was somewhat under 30 hours. In other p v examples it varied from 24 to more than 36 hours. Amme E- The time can be reduced by cutting the low temperature 1 OH; 'H, period to approximately 3 to 6 hours. Note that in Table H3 IV following there are a large number of added examples illustrating the same procedure. In each case the Amine initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. HOCHZOHNH OQHTOXCiHPOXCZHPNHCHYOHZOH Then refluxing was employed until the odor of formalde- Amine hyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to sep- HOCHQCHqNH-CffzCHOHCHz-NHCHgCHzOH arate out all the water, both the solution and condensa- & H HOCH OH NH 0 tion. After all the water had been separated enough xymine T v lene was taken out to have the final product reflux for HOCHOH2NH H several hours somewhere in the range of 145 to 150 (3., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the Amine I- CH5NHOH\ water, had been removed. 25 OHSNHCHFCHQOH Note that as polnted out prevlously, '[hlS procedure 1s illustrated by 24 examples in Table IV.

TABLE IV Strength-of Reac- *Reac- Max. Ex. Resin Amt., Amine used and amount formalde- Solvent used tion tion distill No. used grs. hyde soln. and amt. temp, time, temp,

and amt. 0. hrs. C,

882 Amine A, 296 g 30%, 200 gm Xylene, 500 g. 21-24 24 150 480 Amine A, 148 g Xylene, 480 g -23 27 156 633 -do Xylene, 610g 142 441 Amine B, 176 Xylem-3,3003 28 145 480 do 37], 81 gm. Xylene',4 25'g 34 150 633 do %,100 g... Xylene, 500g 25-27 30 152 882 Amine C, 324 g 37%, 162 g Xylene, 625 gm. 23-26 38 141 480 Amine o, 162 g 30%,100g.-. Xylene, 315g--. 20-21 25 143 633 do a do Xylene,535g 23-24 25 140 473 Amine D, 256 Xylene, 425 g. 22-25 25 148 511 .do Xylene, 450g... 20-21 25 158 665 do X lene, 525 g. 21-26 28 152 441 Amine E, 208 g" Xylene, 400-g. 22-24 26 143 430 -do -do 25-27 36 144 595 .do ,Xylene,500 g. 26-27 34 141 441 Amine F, 236'g Xylene, 400 g' 21-23 25 153 480 .do "do 20-22 28 1.50 511 Mao Xylene, 500 g 23-25 27 155 49s Amine (2,172 g Xylene,400'g 20-21 34 150 542 do Xylene, 450 g 20-24 36 152 547 Amine H, 221 g Xylene, 500 g 20-22 30 148 441 do Xylene, 400 g. 20-29 24 143 595 Amine 1, 172g do Xylene, 450 g 20-22 32 151 391 Amine I, 86 g. 30%, gun Xylene, 300 gm. 20-26 36 147 As to the formulas of the above amines referred to as PART 7 Amine A through Amine I, inclusive, see immediately 0 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3-, we have found it particularly advantageous to use laboratory equipment which permitscontinuous oxypropylation and oxyethylation. The oxyethylation step is, of course, the

same as the oxypropylationv step insofar that two low boiling liquids are handled in each instance. The oxyalkylalion step is carried out in a. manner which is substantially conventional for the oxyalkylation of compounds having labile hydrogen atoms, and for that reason a detailed 7 description of the procedure is omitted and the process will simply be illustrated by the following examples.

Example 16 The oxyalkylation-susceptible compound employed is the one previously described and designated as Example lb. Condensate 1b was in turn obtained from symmetrical di(hydroxyethyl)et-hylene diamine, previously described for convenience as Amine A, and the resin previously identified as Example 2a. Reference to Table III shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 12.02 pounds of this resin condensate were dissolved in 5 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 130 C. to 135 C., and at a pressure of about 15 to 20 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately 1% hours, and then continue stirring for 15 minutes longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 12.02 pounds. This represented a molal ratio of 27.3 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2404. A comparatively small sample less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables V and VI.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a difierent oxide.

Example 2c This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example about 12.02 pounds. The amount of oxide present in the initial step was 12.02 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 12.02 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 24.04 pounds and the molal ratio of ethylene oxide to resin condensate was 54.7 to 1. The theoretical molecular weight was 36.06.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of to pounds. The time period was a little less than before, to wit, only 45 minutes.

Example 3c The oxyalkylation proceeded in the same manner described in Examples 10 and 20. There was no added solvent and no added catalyst. 'The oxide added was 12.02 pounds and the total oxide at the end of the oxyethylation step was 36.06 pounds. The molal ratio of oxide to condensate was 82.0 to 1. Conditions as far as temperature, pressure and time were concerned were all the same'as in Examples 10 and 2c. The time period was one hour.

Example 40 The oxyethylation was continued and the amount of oxide added again was 12.02 pounds. There was no added catalyst and no added solvent. The molal ratio of oxide to condensate was 109 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit 2% hours. The theoretical molecular weight at the end of the prior step was 4808, and at the end of this step 6010. The reaction showed some slowing up at this particular stage.

Example 50 The oxyethylation continued with the introduction of another 12.02 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 7212, and the molal ratio of oxide to resin condensate was 136.5 to 1. The time period, however, was slightly less than before, to wit, 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 12.02

pounds, bringing the total oxide introduced to 72.12 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 84.14 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 9616. The time required for the oxyethylation was the same as in the previous step, to wit, 3 hours.

Example 81:

This was the final oxyethylation in this particular series. There was no added solvent and noadded catalyst. The total amount of oxide added at the end of this step was 96.16 pounds. The theoretical molecular weight was 10,818. The molal ratio of oxide to resin condensate was 218 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was slightly longer than in the previous step, to wit, 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables V and VI, VII and VIII.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables V and VI, it will be noted that compounds 10 through 40c were obtained by the use of ethylene oxide, whereas 41c through c were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed as happens to be the case in Examples through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst and the 7th column shows the amount of solvent employed.

The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VII-I. It is to be noted that the first column refers to Examples lc, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table VI, Examples 41c through 800 are the counterparts of Examples 1c through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, two columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VII. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the ?c series, for example, 370, 40c, 46c, and 77c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds lc through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 370 and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. inversely, those compounds obtained from 46c and 770 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial c series such as 37c, 40c, 46c, and 770, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explana- 30 tion, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with ld, it will be noted that the initial product, i. e., 370, consisting of the reaction product involving 12.02 pounds of the resin condensate, 40.05 pounds of ethylene oxide, 1.0 pound of caustic soda, and 5.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table Vll refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end. of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for through 32d.

it will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VIII.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decol-orized by the use of Clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE V Composition before Composition at end Molal ratio Molec. Ex. No. 1 wt.

O-S O-S Ethl. Pro'pl. Cata- 801- -8 Ethl. Prop]. Cata- Sol- Ethyl. Propl. based ompd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex No lbs. lbs lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. value suscept. suscopt. cmp cmpd.

12. 02 1. 0 5. 0 12.02 1. 0 5. 0 27. 3 2, 404 12. 02 12. 02. 1. 0 5. 0 12. 02 1. 0 5. 0 54.7 3, 606 12. 02 24. 04 1. 0 5. 0 12. 02 1. 0 v5. 0 82.0 4, 808 12. 02 36.06 1. 0 5. 0 12. 02 1. 0 5. 0 109. 0 6,010 12. 02 48.08 1. 3 5. 0 12. 02 1. 3 5. 0 136. 5 7, 212 12. 02 60. 1. 3 5. 0 12. 02 1. 3 5. 0 164. 0 8, 414 12. 02 72. 12 1. 3 5. 0 12. 02 1. 3 I 5. 0 '191. 0 9, 616 12. 02 84. 14 1. 3 5. 0 12. 02 1. 3 510 218.0 10. 818 13.36 1. 0 4. 13.36 .5 4. 25 30. 4 2, 672 13.36 1. 0 4. 25 18. 36 5 4. 25 60. 8 4, 997 13.36 1. 0 4. 25 13.36 .5 4. 25 91. 2 5, 344 13. 36 1. 0 4. 25 13.36 5 4. 25 121. 6 6, 680. 13.36 1. 3 4. 25 13.36 .8 4. 25 152.0 8, 016 13.36 1. 3 4. 25 13.36 8 4. 25 182. 4 9, 352 13.36 1. 3 4. 25 13.36 8 4. 25 .212. 8 10. 688 13.36 1. 3 4. 25 13.36 8 4. 25 243. 2 12,024 13.78 1. 2 4. 0 13.78 1. 2 4. 0 31. 3 2, 756 13.78 1. 2 4. 0 13.78 1. 2 4. 0 62. 6 4, 134 13.78 1. 2 4. 0 13.78 1. 2 4.0 93.9 5, 512 13.78 1. 2 4. 0 13. 78 1. 2 4. 0 125. 2 6, 890 13. 78 1. 2 4. 0 13.78 1. 2 4. 0 156. 5 8, 268 13.78 1. 7 4. 0 13.78 1. 7 4. 0 187. 8 9, 646 13. 78 1. 7 4. 0 13.78 1. 7 4. 0 219. 1 11, 024 13. 78 1. 7 4. 0 13. 78 1. 7 4. 0 240. 8 12, 402 11.86 1. 0 4. 0 11.86 1. 0 4. 0 26. 9 2, 372 11.86 1. 0 4. 0 11.86 1. 0 4.0 53. 8 3, 558 11.86 1. 0 4. 0 11. 86 1. 0 4. 0 80. 7 4, 744 11. 86 1. 0 4. 0 11. 86 1. 0 4. 0 107. 6 5, 930 11.86 1. 3 4. 0 11. 86 1. 0 4. 0 134. 5 7, 116 11.86 1.3 4.0 11.86 1.0 4. 0 161.4 8, 302 11.86 1. 3 4. 0 11.86 1. 0 4. 0 188.3 9, 488 11.86 1. 3 4. 0 11. 86 1; 0 4. 0 242.1 10, 674 12. 02 1. 0 5. 0 12. 02 1. 0 5. 0 13. 7 1,803 12. 02 1. 0 5. 0 12. 02 1. 0 5. 0 27. 4 2, 404 12.02 1.0 5.0 12.02 1.0 5.0 41.1 3,005 1 12. 02 1.0 5. O 12. 02 1. 0 5.0 54.8 3, 606 12.02 1.3 5. O 12. 02 1.3 5.0 68. 5 4, 207 12.02 1.3 5.0 12. 02 1.3 "5.0 82. 2 4, 808 12. 02 1. 3 5. 0 12. 02 1. 3 5. 0 95.9 5, 409 12. 02 1. 3 5. 0 12. 02 1. 3 5. 0 109. 6 6. 010 Oxyalkylation-susceptible.

TABLE VI Composition before Composition at end Molal ratio Molec. Ex. N0. wt.

O-S OS* Ethl. Propl. Cata- Sol- OS* Ethl. Propl. Oata- Sol- Ethyl. Propl. based cmpd., cmpd., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex. N 0. lbs. lbs. lbs. lbs. lbs. 7 lbs. lbs. lbs. lbs. lbs.

12. 02 1. 2 5. 0 12. 02 12. 02 1. 2 5. 0 12. 02 1.2 5. 0 12. 02 24. 04 1. 2 '5. 0 12. 02 1. 2 5. 0 12. 02 36.06 1.2 5. 0 12. 02 1. 2 5. 0 12. 02 48.08 1. 2 5. 0 12. 02 1. 2 5. 0 12. 02 60.10 I 1. 2 5. 0 12. 02 1. 5 5. 0 12. 02 84. 14 1. 5 5. 0 12. 02 1. 5 5. 0 12. 02 108. 18 1. 5' 5. 0v 12. 02 1. 5 5. 0 12. 02 132. 22 1. 5 5. O 13. 36 1. 1 4. 25 13.36 13.36 1. 1 4. 25 13.36 1.1 4. 25 13.36 26. 72 1.1 4. 25 13.36 1. 1 4. 25 13.36 40. 08 1.1 4. 25 13.36 1. 1 4. 25 13.36 53. 44 1.1 4. 25 13.36 1. 1 4. 25 13.36 66. 80 l. 1 4. 25 115. 25 9, 352 13.36 1. 5 4. 25 13.36 93. 52 1. 5 4. 25 161. 12,024 13.36 1. 5 4. 25 13. 36 120. 24 1. 5 4. 25 207. 14, 696 13.36 1. 5 4. 25 13.36 146. 96 1. 5 4. 25 253. 6 16. 032 13. 78 1. 2 4. 0 13. 78 13.78 1. 2 .4. 0 23. 8 756 13. 78 1. 2 4. 0 13. 78 27. 56 1. 2 4. 0 47.6 4,134 13.78 1. 2 4. 0 13.78 41. 34 1. 2 4. O 71. 4 5,512 13. 78 1. 2 4. 0 13. 78 55. 12 1. 2 4. 0 95. 2 6, 890 13.78 1. 2 4. 0 13.78 68. 9 1. 2 r 4. 0 119.0 9,646 13.78 1. 6 4. 0 13.78 96. 46 1. 6 4. 0 166. 6 12, 402 13.78 1.6 4. 0 13.78 124.02 1.6 4.0 214. 2 15,158 13.78 1. 6 4. 0 13.78 151. 58 1. 6 4. 0 262. 6 16, 536 11.86 1.1 4. 0 11.86 .11. 86 1.1 4. 0 20. 4 2, 372 11.86 1.1 4.0 11.86 23. 72 1.1 4.0 40. 8 3, 538 11.86 1.1 4.0 11.86 35.58 1.1 4.0 61.2 4,744 11.86 1. 1 4. 0 11.86 47. 44 1. 1 r 4. 0 81. 6 5, 930 11. 86 1.1 4. 0 11.86 50. 30 -1. 1 4. 0 102.0 7, 116 11.86 1. 5 4. 0 11. 86 83.02 1. 5 4. 0 142.8 8, 302 11.86 1. 5 4. 0 11.86 106. 74 1. 5 4. 0, 183. 6 9.488 11.86 1.5 4. 0 11. 86 130. 46 1. 5 "4. 0 224. 4 10, 674 12. 02 1.1 5. 0 12. 02 6.01 1. 1 5. 0 10. 36 1, 803 12. 02 1.1 5. 0 12. 02 12. 02 '1. 1 5. 0 '20. 8 2, 404 12. 02 1. 1 5. 0 12. 02 18.03 1. 1 5. 0 31. 2 3,005 12. 02 1.1 5. 0 12. 02 24.04 1.1 5. 0 41.6 3, 606 12. 02 1.1 5. 0 12. 02 30. 05 1. 1 5. 0 51. 8 4. 205 12. 02 1. 5 5. 0 42.07 1. 6 6.0 72. 6 5. 409 12. 02 1. 5 5. 0 54109 "1. 5 5. 0 93.4 6, 611 806.. 10... 12.02 1.5 5.0, .6611, .15 5.0 114.0 7.813

*0xyaikylation-susceptible.

Max. Max. Solubility 116:1. te ngx, pres}. 'Igme, o. .s. rs.

p Water Xylene Kerosene 130-135 30-35 Insoluble Soluble. 30-35 do Do. 30-35 Do. 30-35 Do. 30-35 Do. 30-35 D0. 15-25 Insoluble 15-25 D0. 15-25 Soluble. 15-25 Do. 15-25 D0. 15-25 Do. 15-25 Do. 15-25 D0. 20-25 Insoluble. 20-25 Do. 20-25 Do. 20-25 Soluble. 20-25 Do. 20-25 Do. 20-25 D0. 20-25 Do. 20-25 Insoluble 20-25 D0. 20-25 Do. 20-25 D0. 20-25 Do. 20-25 Dispersible. 20-25 Soluble. 20-25 Do. 10-15 Insoluble 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Dispersible. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 Insoluble. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Dlspersible 10-15 DO. 10-15 Soluble. 20-25 D0. 20-25 Do. 20-25 Dispersible. 20-25 Insoluble. 20-25 Do. 20-25 Do. 20-25 Do. 20-25 Do. 20-25 D0. 20-25 D0. 20-25 Do. 20-25 Do. 20-25 Do. 20-25 Do. 20-25 D0. 20-25 Do.

PART 8 used. If for any reason the reaction does not proceed The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing moncepoxides in Part Seven immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be sufficient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in comrapidly enough with the diglycidyl ether or other analog- 7 cos reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

. It goes without saying that thereaction can take place in an inert solvent i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conven iently an aromatic solvent such as Xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be ren-. dered solvent-free and it is necessary that the solventbe readily removed as, for example,by theme of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not-oxyalkylation-susceptible. It is easy venough to select a suitable solvent if required many. in-

stance but everything else being equal, the solvent chosen should he the most economical one.

Example la The product was obtained by "reaction between the diepoxide previously described as diepoxide 3A and oxyin order to examine the physical properties. The material was an amber, or 'lig'htreddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particualkylated resin condensate 2c. Oxyalkyiated condensate 5 larly i a i tur f 80% xylene and 20% methanol. 26 has been described in PYeViOl-IS Part Seven and However, if the material was dissolved in an oxygenated Obtained y the oxyelhylalieh f condensate The solvent and then shaken with gluconic acid it showed preparation of condensate lb was described in Part 6, a d fi i tendency to di e d, o f a 1, Preceding Details have been included regard to both and particularly in a xylene-methanol mixed solvent as P Condensate 1b in turn, was 0bi?1hed from previously described, with or without the further addition metrical di(hydroxyethyl) ethylenediamine and has been f a li tl t described as amine A. T resin p y res"! Generally speaking, the solubility of these derivatives Which in turn, Was Obtained from p y p is in line with expectations by merely examining the solnol and formaldehyde. p ubility of the preceding intermediates, to wit, the oxyal- In y event, 361 grams of the oxyalkyleted kylated resin condensates prior to treatment with the didensate previously identified as were dissolved 1n apid Th m i l f com-Se, vary f proximately an equal Welght of Xylene- About 3-5grams tremely water-soluble products due to substantial oxyf Sodium methylate Were added as catalyst 50 the ethylation, to those which conversely are water-insoluble t tal amount of Catalyst P h lllehldlhg l'esldlle11 eatabut xylene-soluble or even kerosene-soluble due to high y from the Prior oxyalkylatloh: e abollt grams- 20 stage oxypropylation. Reactions with diepoxides or 17 grams of diePOXIde W hllXed Wlth qb polyepoxides of the kind herein described reduce the weight of xylene. The 1n1t1al addltion of the diepoxide hydrophile properties and increase the hydrophobe propsolution was made after raising the temperature of the erties, i. e., generally make the products more soluble in reaction mass to about 104 C. The diepoxide was added kerosene or a mixture of kerosene and ylene, or in yslowly over a period of one ho r- Durmg t s time the lene, but less soluble in water. Since this is a general temperature was aOwed to rise 10 abOllt rule which applies throughout, for sake of brevity future mixture was allowed to reflux at about 134 C. using a reference t solubility ill b itted, phase-separating trap. A small amount of xylene was The procedure employed, of course, is simple in light removed by m an of a P S P g p 50 e of what has been said previously and in effect is a profillXihg tembefaime fhse gradually about The cedure similar to that employed in the use of glycide or mixture was refluxed at thls temperat re or abo t 5 methylglycide as oxyalkylating agents. See, for example, hours. At the end of this penod the xylene which had Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952 been removed by means of the phase-separating trap was to De Groom, returned to the mixture. A small amount of material Various examples obtained in substantially the same was withdrawn and the xylene evaporated on a hot plate manner are enumerated in the following tables:

TABLE IX Ex. Oxy. Amt, Diep- Amt., Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (N80011:), lane, ratio reaction, temp., Color and physical state densate used grs. grs. hrs C.

361 3A 17 3.8 378 2:1 4 155 Reddish-amber resinous mass. 301 3A a. 5 3. 1 310 2: 1 4 160 Do. 267 3A 17 2. s 284 2: 1 4 153 D0. 276 3A 8. 5 2.8 285 2:1 5 145 D0. 415 3A 8. 5 4. 2 424 2:1 4 160 Do. 240 3A 17 2. 6 257 2:1 4 160 Do. 481 8A 17 5.0 498 2:1 5 150 Do. 257 8A 8. 5 2. s 276 2: 1 5 152 D0. 237 3A 17 2. 5 254 2:1 5 146 Do. 474 3A 8. 5 4. 8 483 2:1 5 145 D0. 481 3A 17 5. 0 498 2:1 5 145 Do. 270 3A 8. 5 2. s 279 2: 1 4 152 Do. 421 3A 8.5 4. 3 430 2:1 4 150 Do. 481 3A 8. 5 4. 9 490 2: 1 4 154 Do. 3.4 1.7 1.4 2:1 4 150 D0.

TABLE -X Ex. Oxy. Amt, Dlep- Amt, Catalyst Xy- I Molar Time of Max. No. resin congrs. oxide grs. (NaOCHr), lens, ratio reaction, temp, Color and physical-state densate used grs. grs. hrs. C.

361 B1 27.5 3.9 389 2:1 4. 5 150 Reddish-amber resinous mass. 301 B1 13. s 3. 2 315 2:1 4. 5 e 150 Do. 257 B1 27. 5 3. 0 295 2:1 4. 5 157 Do. 276 B1 13. 5 2. 9 290 2: 1 4. 5 155 Do. 415 Bi 13.8 4. 3 429 2: 1 5 Do. 240 B1 27. 5 2. 7 1 268 2:1 4 152 Do. 481 B1 27.5 5.1 509 2:1 5 Do. 267 B1 13.8 2.8 251 2: 1 4 Do. 237 B1 27. 5 2. 7 265 2: 1 4 156' Do. 474 B1 13.8 4. 9 488 2:1 4. 5 150, D0. 481 B1 27. 5 5. 1 509 2:1 5 148 Do. 270 B1 13. s 2. 8 254 2:1 5 145 D0. 421 B1 13.8 4. 4 435 2:1 5 145 .Do. 481 B1 13.11 5. 0 495 2: 1 5 147 Do. 138 B1 2. s 1. 4 141 2: 1 4 150 D0.

i TABLE xr Prob. mol. Ex. No. Oxyalkyl. weight of Amount Amount of resin conreaction product, grs. solvent densate product TABLE XII Prob. mol. Ex. No. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product 5, 890 2, 945 1, 473 11, 570 2, 314 1, 157 17, 150 3, 430 1, 715 5, 360 2, 680 1,340 10, 170 2, 034 1, 017 11, 240 2, 248 1, 124 5, 290 2, 645 l, 323 19, 53 3, 906 l, 953 10, 160 2, 032 l, 016 11, 360 2, 272 1, 136 17,370 3, 474 1, 737 19, 770 3, 954 1, 977 28, 1-70 2, 817 1, A09

At this point it may be desirable to direct attention to two facts, the first being that we are aware that other diepoxides free from an aromatic radical as, for example,

epoxides derived from ethylene glycol, glycerin, or th like such as the following: I r

H H n H H n H 7-8- O V H O H H H H 1 Ho-ooc00c -(;H

may be employed to replace the diepoxides herein described. However su'ch derivatives are not included as part of the instant invention. 3 1

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or usebenzene entirely. Also, we have foundiit desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine) CHz(Resin)CI-Iz(Amine) '49 If such product is subjected to oxyalkylation reaction involves the phenolic hydroxyls of the resin structure and, thus, can be depicted in the following manner:

(Amine) CH2 (Oxyalkylated Resin) CH2 (Amine) Following such simplification the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine) CH:(Oxyalkylated Resin)OH (Amine) D .G. E.

. I (Amine)OH1(Oxyalkylated Resin) OHKAmine) in which D.G.E. represents a diglycidyl ether as specified.

As has been pointed out previously, the condensation reaction may produce other products, including, for example, a product which may be indicated thus in light of what has been said previously:

[ (Amine) CHz(Resin) 1 This product, since it is susceptible to oxyalkylation by means of the oxyalkylatedphenolic hydroxyl groups and depending'on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[(Oxyalkylated(/1mine) CHz(Resin)] When a di glycidyl ether is employed one would obviously obtain'compounds in which two molecules of the kind described immediately preceding are united in a manner comparable to that previously 'described, which may be indicated thus;

I -[0xyalkylated(Amine)OHa(Resin)] D.G.E.

l Oxyalkylated(Arnine) OH; (Resin) Likewise, it is obvious that the two different types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

' (Amine) OH,(Oxyalkylated Resin) CH, (Amino) I I D.G.E.

l Oxyalkylated(Amine)CHz(Amine) Actually, the product obtained by reaction with 'a diglycidyl ether could show. considerably greater complexity dueto the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOSIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESING BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESING BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 